New series of organic compounds



United States Patent 2,931,816 NEW SERIES or ORGANIC COMPOUNDS Werner Richard Boehme, Somerville, N.J., assignor to Ethicon, Inc., a corporation of New Jersey No Drawing. Application November 8, 1957 Serial No. 695,217

10 Claims. (Cl. 260-3462) represented by the following general structural formula:

wherein X is an ethylene or vinylene group and R and R" are, interchangeably, alkyl, especially lower alkyl, aralkyl,

or acyl groups. Examples of suitable alkyl subst'itnents phenyl aliphatic carboxylic acid, such as an alkoxy'cin-j namic acid, e.g. methoxy cinnamic acidor ethoxycinnamic acid; a pyridine carboxylic acid such as nicotinic or iso-' n cotinic acid; a. thiophene carboxylic a cid such as thiopheneQ-carboxylic acid; or an arylsulfonic acid such;

asbenzcnesulfonic acid .or p-toluenesulf onic acid;

The hexahydroand tetrahydrophthalans of this invention aremiscible .with alcohol and hydroalcoholic mixtures, and are non-irritating. Theypossess pleasant odors and, for this reason, lend themselves to use as ingredients in perfume, :cologne and scented cosmetic formulations, for example in cold creams, vanishing creams, astringent lotions, hand lotions, etc. in quantitiesranging from about 0.5% to about 20%.

' The tetrahydrophthalans of this invention maybe prepared by condensing cyclopentadiene or dicyclopentadiene with a Z-RO-S-R'O-2,5-dihydrofuran, and,'if desired, conerting' the product so obtained to the corresponding hexahydrophthalan by catalytic hydrogenation. TheR and R substituents in the 2,5 positions of the dihydrofuran starting material may be, interchangeably, alkyl,

' 1 2,931,816 1C Patented Apr. 5, 1960 such purpose are the liquid hydrocarbons having a boiling point in excess of 70 C., such as for example, toluene, benzene, xylene. kerosene, dioxane, chlorbenzene, dichlorobenzene, carbon tetrachloride, etc. Thereaction is conducted at room temperature or, preferably, at elevated temperature, i.e. from about 100 C.- to about 200 C., at atmospheric pressure, or, preferably, in a closed vessel under pressure and, if desired, in the presence of an inert gas, e.g. nitrogen.

Hydrogenation of thetetrahyd'rophthalans to the corresponding hexahydrophthalans is preferably carried out by catalytic means, that is to say with hydrogen in the presence of a catalyst selected from the metalsof the eighth group of the periodic system, such as nickel, for example, Raney nickel; palladium, platinum or rhodium.

They may be employed on carriers such as barium car-' bonate, kieselguhr or charcoal, in the form of special preparations sucb'as palladium black, or preferably as oxides, such as platinum oxide. The reduction is most advantageously carriedout in the-presence of a solvent such as a lower alkanolQfor example methanol or ethanol and, if so desired, under pressure.

aralkyl or acyl groups such as one of those defined here- 1 .The' starting materials used in the preparation of the compounds of this invention are known or may be pre pared by methods known to those skilled in the art. In a. general way, the 2,5-dialkoxy-2,S-dihydrofurans are prepared by electrolysis of furan in an appropriate alcohol, i.e. lower alkanol in the presence of an electrolyte such as sulfuric acid or ammonium bromide. Alternatively, thesestarting materials may be prepared by reacting furan at low temperature in a solution of a lower alkanol with a halogen such as bromine or chlorine. The 2,5-diacyloxy-2,5-dihydrofuran starting materials may be prepared by treating furan with bromine in the presence of an appropriate acid, i.e. one of those referred to hereinabove or with a tetravalent lead salt of the appropriate acid, such as lead tetraacetate. The directions for preparing -various 2,5-dialkoxy-2,S-dihydrofurans and 2,5- dia'cyloxy-2,5-dihydrofurans are available in the literature, for example in United States Patent 2,714,576 to Clauson-Kaas (dialkoxy) and in Act. Chem. Scand. 1,

379-81 (1947), and Kgl. Danske. Videnskab. Selskab.

' The following examples are submitted as being illustra tive of the inventiombut are not intended to be limitative v01'1 its SC'OPE.

Example I A solution of 55 parts by weight of freshly-distil1edcyclopent'a'diene, 87 parts by weight of 2,5-dirnethoxy-2,5-

Example I] a. by... We ht f .3:di h y- J-endomethylene-4,7,8,9-tetrahydrophthalan is hydrogenated in 100 parts by volume of ethanol at 50 pounds initial hydrogen pressure in the presence of palladium oxide. Fractionation through a Vigreux column after removal of the catalyst gives 15.0 parts by weight of l,3-dimethoxy- 4,7-endomethylenehexahydrophthalan, a colorless liquid, B.P. 121-122 C./1l mm., 11 1.4764,

196 parts Bo-87 C./0.70.8 mm., 1.47 60.

3 Example III 7 the yellow liquid is distilled to give l,3-diethoxy-4,7-endomethylcue-4,7,8,9-tetrahydrophthalan which boils at Example I V A mixture of 7.9 parts by weight of 2,5-diisopropoxy- 2,5-dihydrofuran, 5.3 parts by volume of cyclopentadiene and 0.10 part by weight of hydroquinone is heated in a sealed tube at 160 C. for a period of 24 hours. The resulting liquid is distilled to give 1,3-diisopropoxy-4,7-en-- domethylene-4,7,8,9-tetrahydrophthalan,' B.P. ill-121 C./2.4 mm.

- Example V White beeswax Paraflin Ceresin White mineral oil Borax Water 1,3 dimethoxy 4,7-endomethylene hexahydrophthalan The borax is dissolved in hot water. The waxes are melted together and the mineral oil is added, the temperature being kept at about 70 C. The borax solu-- tion is added with stirring. The mixture is cooled and the phthalan perfume is added with stirring.

Example VII 1,3 dimethoxy 4,7-endomethylene-hexahydrophthalan V Phenylethyl alcohol 1.0 Benzyl acetate 1.0 Ethyl alcohol, U.S.P., q.s 100.0

The hexahydrophthalan is mixed with the phenylethyl alcohol and benzyl acetate, and a sufiicient quantity of ethyl alcohol is added to make a 100 ml. solution.

Example VIII Parts Terpineol 20 Heliotropine 20 Vanillin 10 Coumarin 10 Benzyl acetate 10 1,3 dimethoxy 4,7 endomethylenehexahydrophthalan Synthetic French rose 5 Tuberose, absolute (liquid) 5 Jasmine (synthetic) To make perfume 100 4 Example IX Synthetic French rose 10 Heliotropine 10 Cinnamic alcohol 20 Bergamot oil 10 Phenylacetaldehyde (50%) 20 Jasmine (synthetic) 10 Terpineol 10 1,3 diisopropoxy 4,7-endomethylene-1,7,8,9-tetrahydrophthalan 10 To make perfume Example X Benzyl acetate 15 Linalyl acetate 10 Linalool 10 Hydroxy-citronellol 10 Jasmine (absolute) 5 Phenylethyl alcohol 10 Rhodinol 10 Heliotropine 10 1,3 dibenzyloxy-4,7-endomethylene-4,7,8,9-tetrahydrophthalan Benzyl alcohol, sufiicient quantity to make perfume 100 What is claimed is:

1. A member selected from the group consisting of compounds of the general formula wherein X is a member of group consisting of ethylene 4. 1,3 di lower alkoxy-4,7-endomethylene-hcxahydrophthalan. 5. 1,3-di-lower alkyl carbonyloxy-4,7-endomethylenehexahydrophthalan.

6. 1,3 dimethoxy 4,7-endomethylene-4,7,8,9-tetrahydrophthalan.

7. 1,3 1 dimethoxy 4,7 endomethylenehexahydroplr thalan. V I 8. 1,3 diethoxy 4,7 endornethylene-4,7,8,9-tetrahydrophthalan.

- 9; 1,3 diisopropoxy 4,7 endomethylene 4,7,8,9-"

tetrahydrophthalan.

10. 1,3 dibenzyloxy 4,1 endometbylene -"4,7,s,9-'

tetrahydrophthalan.

References Cited in the file of this patent Kononov et al.: Chemical Abstracts, vol. 48 (1954), col. l0377e.

Brace: J. Amer. Chem. Soc., vol. 77 (1955), pp.

I-Iufiord et al.: J.A.C.S., vol. 74, pp. 3014-18 (1952). Norton: Chemical Reviews, vol. 31 (1942), pp. 320-v $06. 

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OF THE GENERAL FORMULA 